Process of preparing hydrocarbons



' Patented 'Sep t. 12, 1933 tasti gs-p PREPARING nynaoe meofisa f 1 i Ivan, Gubelmann land ClydelO, Henke; Sputh .j Milwaukee; Wis.,- assigncrs, ,by mesne assignments to Newport Industries, Inc; a corpo l v ration; of Delaware 1 Noprawinga Application Ma ch 18, 19cc v Serial-"N0.'348,123

This invention relates, to j a process" of preparing hydrocarbons from abietic acid or abietic acid containing materialsand relates more particularly to the catalytic decomposition of abietic ,5 acid or. volatile mat'erial containing the abietic acid radical bypassinga gascontaining abietic acid overbrthrou'gh a catalytic mass vated temperature. W a

, I It is an objeetiof this invention to provide a method of obtainingvaluable hydrocarbons from abietio acidcontaininlimaterial in an economically practical manner.

c Other and further important objects of this lowing descriptionand appendedclaims.

Among the known hydrocarbons whichcan be 'fyields, are retene; and jabie'tene, Otherhydrocarbonslthat have not asfyet been completely 2 identified have. alsofbeenflprepared by this method.

The processicomprise's briefly passinga gaseous mixture containing thevapors of'abietic acid through a catalytic massmaintained atan elevatedtempera'ture; ,JThe f gaseous mixturemay contain, inadditi'on'j'to abieticacid, steam; air,

ammonia, hydrochloric acid gas and the like.

Preferably, a mixture consisting principally, of steam and abietic acidvapors, is used.

The catalytic-mass that is employed may be any one of a large number of catalystswhich are employed for a similar purpose. The most prob able reaction involved is the removal of CO2 and of hydrogenand alkyl radicals Depending upon the particular reaction to be brought about, a specific catalyst is selected, since'difierent catalysts have somewhat different catalyticactivities. .The use of charcoal is particularly efiective in the removal of carbon dioxide to produce abietene.

valuable'in efiecting a dehydrogenation or a dealkylation.

a wide variety of difierent materials may be used as catalysts and these materials may be prepared in various ways. Likewise, mixtures of two or The temperatures employed for thereactionsare subject to wide variation, and temperatures Point of 1701c. is obtained. 1 v

1 While, weprefer to work at atmospheric presinvention' will, become apparent from the fol- W The use of vanadium pentoxide is particularly a In this process, as in other catalytic processes,

from 350 to 650 C. have beenused. The temperature to beemployed will depend upon the "catalyst used and uponithe particularproduct desired For instance, infthe use of vanadium pentoxideas the catalyst if a temperature of 520 C. is 'employed,re tene is produced; -When using,

660] C. another hydrocarbon having a melting I sure or 'withju'st -sufficient pressure on the appa ratus to cause jaflow of vapors-fthrou'gh it," higher I for lower pressures may be employ'edand are contained within the scope fof this invention;

" The invention in its broadest aspectcomprises 7 n pr-o 'sses for producing hydrocarbons byr'the zc 5 catalytic decomposition' of abietic acid containobtained by the present process inrelativelyj ood ing material in vapor phase at an elevatedtem perature'.- The "following' examples: are given merely byfway'of' illustration and-it is to be understood that the invention is not limited to Z these specific examples."

' These vapors are then brought into contact with activated charcoalheld at a temperature of 410 C, The treated vaporsare thenfcondensed, to,

obtain an'oil which contains only very small 5 quantities'of undecomposed abietic acid. The, crude oil as obtained has a specific gravity of '0.96'( at'-20 C. and distills for the most part between 330 and 360? Cg The main constituent of this oil is abietene; V

If instead of abietic acid ethyl abietate is ,va-,.-:

porized and contacted with activated charcoal accordingto the above example, the product ob the most part of abietena If in the above example the catalyst is omitted,

the condenser fills'with whitecrystalswhich are essentially abietic acid.

Example II Abietic acid is vaporized as before by passing. steam throughthe'molt'en abietic acid at 220 to 240 ,C. Thesavaporsare brought into contact with vanadium pentoxide by passing the vapors through it. The vanadium pentoxide is held at a temperature of. 520 C. The decomposition products are then condensed to produce a product inthe form of an oily paste, comprising a mixture of hydrocarbons'and some undecomposed abieticacid. The oily paste is separated'from the water and then fractionally distilled in vacuo.--

.itained is substantiallythe same, consisting for T [1 ,926,616 a Y 60 the same catalyst and'temperatures of about at'an elized from acetic acid or alcohol.

, ther catalytically.decomposed as above to give."

The fraction distilling between 190 and 240 C.

further quantities of retene.

If instead of abietic acid anathema is' va porized and contacted with vanadium pentoxide according to the above example, the product obtained is substantially the samefrom 'which retene. may be isolated'as above.

7 Example 1H J The vapors of abietic acid are producedlas in Examples I and II, with abietic acidandfsteam and then passed over vanadium. pentoXide held at a temperature or 600 C. .The vapors are then condensed and the condensate worked upjas in Example I I. The' product obtained is difierent from ,thatobtained in EXarnpleII, and by combustion analysisis found to'contain 92.7% carbon and 6'.86%"hydrogen. The product has'a melting point of 169 to l'lOfC. afteri'it has been recrystallized from glacial acetic acid; The compound is most probably iso-propyl phenahthrene.

We are awareth'at manyclianges may be made in the above, exarnples' to produce various mixtures of hydrocarbons asabovedescribed. Other catalyststhan thosespecified infthe examples may be employed andvarious temperatures, depending upon the product desired. Furthermore,

. ,instead of using emetic acid as such, 'abietic' acid v containing materials such as woodor gumrosin,

or purified rosinffrom j'the crude rosin 'may be used. 'f

Any of the various isomersoi" abi'etic acid which are commonly referred t'o'generic'ally'as"abietic acids, for instance, sa-pinic, pyro-abietic, pineabietic, and pimaric acids,.may be used. Furthermore; instead of'the' ac'id form, any'or its derivatives, such asv esters .'or anhydridespmay, be

used, so-long as the derivative retains the property of vaporizing at the temperatures indicated.

We are aware that numerous details of the process may be varied through a wide range without departing'from the principles of this invention, and we, therefore, do notpurpose'limiting ,thejpatent granted hereon otherwise than necessitated by the prior art.

We claim as our invention:

1. In the process of preparing hydrocarbons 'bythe thermal decomposition of abietic acid containing material the step which comprises decomposing said material while in the vapor phase by passing the vaporsover activated-charcoal at temperatures between 350 and650 C.

2. The process of producing abietene which I comprises vaporizing abietic acid, and passing the vapors into contactwith activated charcoal held I at-a' te mperature of 410 degrees C.

. 3..The process. of preparingv selected from the group'consistingof vanadium pent'oxide, zinc oxide, chromium oxide, manganes'e 'oxidef copp'er oxide, molybdic acid anhydride and charcoalv at temperatures between 350 and 650 C v 4. The process of producing hydrocarbons,

v hydrocarbons, 'which comprises passing-vapors of abietic acid 'containing material into contact with a'catalyst which compris'e's'passingvapors containing abietic' acid and steam-into contact with a catalyst selected, from a group consisting of vanadium pentoxide, zinc oxide, chromium oxide, manganeseoxide; copper oxide, 'mol'ybdic acid. anhydride andcharcoal at temperatures "between 350 and.

5. The process" of; producing hydrocarbons, which comprises passing steam through molten abietic acidat temperatures from 220Pto 240 C.,

contacting the vapor produced with vanadium. i 15.

pentoxide held at a temperature between 520 ,and 600 C, condensing the decomposition products formed and purifying said products.

' CLYDE'YO. V s 

